WO2021196558A1 - Ternary refrigeration composition and refrigeration device comprising same - Google Patents

Ternary refrigeration composition and refrigeration device comprising same Download PDF

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Publication number
WO2021196558A1
WO2021196558A1 PCT/CN2020/120213 CN2020120213W WO2021196558A1 WO 2021196558 A1 WO2021196558 A1 WO 2021196558A1 CN 2020120213 W CN2020120213 W CN 2020120213W WO 2021196558 A1 WO2021196558 A1 WO 2021196558A1
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ternary
component
refrigeration composition
refrigeration
composition
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PCT/CN2020/120213
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French (fr)
Chinese (zh)
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钟权
赵桓
雷佩玉
黄宇杰
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珠海格力电器股份有限公司
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Publication of WO2021196558A1 publication Critical patent/WO2021196558A1/en

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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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B1/00—Compression machines, plants or systems with non-reversible cycle
    • 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
    • C09K2205/22—All components of a mixture being fluoro compounds
    • 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 relates to the technical field of refrigeration materials, in particular to a ternary refrigeration composition and a refrigeration device containing the same.
  • R290 Propane
  • ODP ozone depletion potential
  • GWP extremely low global warming potential
  • R290 has been used in air-conditioning systems, refrigerators and small freezers in Germany, Sweden and other EU countries.
  • India has also realized the marketization of R290 air conditioners.
  • Domestic companies such as Gree, Midea and Haier took the lead in launching the R290 air-conditioning production line transformation project, and several production lines have been built.
  • R290 is classified as a Class 3 flammable refrigerant, and for safety reasons, it cannot be widely promoted in the market.
  • the main purpose of the present invention is to provide a ternary refrigeration composition and a refrigeration device containing the same, so as to solve the problem that the existing refrigeration composition cannot guarantee low GWP, low ODP and good thermodynamic properties while also having low flammability. Performance issues.
  • a ternary refrigeration composition is provided.
  • the ternary refrigeration composition is composed of a first component and a second component, wherein the first component is fluoroethane, and the first component is fluoroethane.
  • the two components are selected from any two of 1,1-difluoroethane, difluoromethane and 2,3,3,3-tetrafluoropropene.
  • the second component is 1,1-difluoroethane and difluoromethane
  • the ternary refrigeration composition includes 76-88% of the first component, calculated as a mole percentage of the ternary refrigeration composition, 4-20% 1,1-difluoroethane and 4-12% difluoromethane.
  • the ternary refrigeration composition includes 84 to 88% of the first component, 4 to 12% 1,1-difluoroethane and 4 to 12% of the ternary refrigeration composition in terms of mole percentage. Fluoromethane.
  • the ternary refrigeration composition includes 76-80% of the first component, 12-20% of 1,1-difluoroethane and 4-8% of difluoroethane. Fluoromethane.
  • the second component is difluoromethane and 2,3,3,3-tetrafluoropropene
  • the ternary refrigeration composition includes 68-88% of the first Components: 4-20% difluoromethane, 4-28% 2,3,3,3-tetrafluoropropene.
  • the ternary refrigeration composition includes 68 to 88% of the first component, 4 to 8% of difluoromethane and the balance 2,3,3,3 -Tetrafluoropropylene.
  • the second component is 1,1-difluoroethane and 2,3,3,3-tetrafluoropropene.
  • the ternary refrigeration composition includes 60% by mole percentage of the ternary refrigeration composition. ⁇ 88% of the first component, 4 ⁇ 12% of 1,1-difluoroethane and 4 ⁇ 36% of 2,3,3,3-tetrafluoropropene.
  • the ternary refrigeration composition includes 60-88% of the first component, 4-8% of 1,1-difluoroethane and the balance of 2, 3,3,3-Tetrafluoropropene.
  • the refrigeration device includes a refrigerant, and the refrigerant includes the ternary refrigeration composition provided in the present application.
  • the environmental protection characteristics and thermodynamic properties of fluoroethane are similar to R290, but the flammability is lower than R290.
  • fluoroethane with the second component whose flammability is Class 2 or Class 2L Use, can make the refrigeration composition have lower GWP and good thermodynamic properties, as well as lower flammability level, improve its safety; at the same time, the ODP value of the above-mentioned ternary refrigeration composition is zero, even if it is used for a long time. Cause damage to the ozone layer.
  • the above-mentioned ternary refrigeration composition has a lower GWP, ODP is 0, and the flammability is Class 2, and the capacity and energy efficiency of the unit using the ternary refrigeration mixture is equivalent to that of the unit using the R290 refrigerant.
  • the existing refrigeration composition cannot guarantee low GWP, low ODP and good thermodynamic properties, but also has the problem of low flammability.
  • the present application provides a ternary refrigeration composition consisting of a first component and a second component, wherein the first component is fluoroethane and the second component is Any two selected from 1,1-difluoroethane, difluoromethane and 2,3,3,3-tetrafluoropropene.
  • the environmental protection characteristics and thermodynamic properties of fluoroethane are similar to R290, but the flammability is lower than R290.
  • the refrigeration composition can be made It has low GWP and good thermodynamic properties, and a low flammability level, which improves its safety in use; at the same time, the ODP value of the above-mentioned ternary refrigeration composition is zero, even if it is used for a long time, it will not cause damage to the ozone layer.
  • the above-mentioned ternary refrigeration composition has a lower GWP, ODP is 0, and the flammability is Class 2, and the capacity and energy efficiency of the unit using the ternary refrigeration mixture is equivalent to that of the unit using the R290 refrigerant.
  • Difluoromethane has good thermal performance, environmental performance, safety and market availability, but as a refrigerant alone, R32 will cause the problem of excessive compressor discharge temperature.
  • the second component is 1,1-difluoroethane and difluoromethane
  • the ternary refrigeration composition includes 76-88 % First component, 4-20% 1,1-difluoroethane and 4-12% difluoromethane.
  • Using the mixture of 1,1-difluoroethane and difluoromethane as the second component can reduce the compressor discharge temperature during the refrigeration process, and at the same time limit the amount of each component in the ternary refrigeration composition within the above range. It is beneficial to further improve the refrigeration effect of the ternary refrigeration composition and reduce its flammability.
  • the ternary refrigeration composition comprises 84 to 88% of the first component, 4 to 12% 1,1-difluoroethane, and 4 to 12% based on the mole percentage of the ternary refrigeration composition.
  • Difluoromethane; or, based on the mole percentage of the ternary refrigeration composition the ternary refrigeration composition includes 76 to 80% of the first component, 12 to 20% of 1,1-difluoroethane and 4 to 8% difluoromethane.
  • the amount of the first component the amount of 1,1-difluoroethane and difluoromethane in the second component is more accurately controlled, so as to further reduce its flammability and improve its cycle performance.
  • the second component is 1,1-difluoroethane and 2,3,3,3-tetrafluoropropene, and is calculated as a mole percentage of the ternary refrigeration composition.
  • the primary refrigeration composition includes 60-88% of the first component, 4-12% of 1,1-difluoroethane and 4-36% of 2,3,3,3-tetrafluoropropene.
  • Using the mixture of 1,1-difluoroethane and 2,3,3,3-tetrafluoropropene as the second component while limiting the amount of each component in the ternary refrigeration composition within the above range is beneficial to further Improve the refrigeration effect of the ternary refrigeration composition and reduce its flammability.
  • the ternary refrigeration composition includes 60% by mole percentage of the ternary refrigeration composition. ⁇ 88% of the first component, 4 ⁇ 8% of 1,1-difluoroethane and the balance of 2,3,3,3-tetrafluoropropene.
  • the second component is difluoromethane and 2,3,3,3-tetrafluoropropene
  • the ternary refrigeration composition includes 68 to 88% of the first component, 4 to 20% of difluoromethane, 4 to 28% of 2,3,3,3-tetrafluoropropene.
  • Using the mixture of 1,1-difluoroethane and 2,3,3,3-tetrafluoropropene as the second component can reduce the compressor discharge temperature during the refrigeration process, further reduce GWP, and improve its environmental performance; Limiting the amount of each component in the ternary refrigeration composition within the above range can combine the properties of the first combination and the second component, and further improve the overall performance of the ternary refrigeration composition.
  • the ternary refrigeration composition includes 68% by mole percentage of the ternary refrigeration composition. ⁇ 88% of the first component, 4 ⁇ 8% of difluoromethane and the balance 2,3,3,3-tetrafluoropropene.
  • the refrigeration device includes a refrigerant, wherein the refrigerant includes the above-mentioned ternary refrigeration composition.
  • the above-mentioned ternary refrigeration composition has lower GWP, ODP is 0, and flammability is Class 2. Applying it to the refrigeration device can obtain higher capacity and energy efficiency, and at the same time can make the refrigeration device have higher safety and environmental protection.
  • thermophysical properties of the components involved in the examples are shown in Table 1.
  • composition of the ternary refrigeration composition prepared in each example is shown in Table 2.
  • Example 25 R161 R32 R1234yf 0.6/0.04/0.36
  • Example 26 R161 R32 R1234yf 0.64/0.04/0.32
  • Example 27 R161 R32 R1234yf 0.64/0.08/0.28
  • Example 28 R161 R32 R1234yf 0.68/0.04/0.28
  • Example 29 R161 R32 R1234yf 0.68/0.08/0.24
  • Example 30 R161 R32 R1234yf 0.72/0.04/0.24
  • Example 31 R161 R32 R1234yf 0.72/0.08/0.2
  • Example 32 R161 R32 R1234yf 0.72/0.12/0.16
  • Example 33 R161 R32 R1234yf 0.76/0.04/0.2
  • Example 34 R161 R32 R1234yf 0.76/0.08/0.16
  • Example 35 R161 R32 R1234yf 0.76/0.12/0.12
  • Example 36 R161 R32 R1234yf 0.8/0.0
  • the ternary refrigeration composition in Examples 1 to 49 was used instead of R290 as the air-conditioning refrigerant.
  • the selected design conditions are: the evaporator outlet temperature is 283.15K, the condenser outlet temperature is 313.15K, the gas phase at the evaporator outlet is in a superheated state, and the superheat is 5K, and the liquid phase at the condenser outlet is in a supercooled state.
  • the cooling degree is 5K, and the adiabatic efficiency of the compressor is 0.75.
  • the ternary refrigeration composition in the above-mentioned embodiment and the cycle performance parameters of R290 refrigerant in the refrigeration system are used for theoretical calculations, and the GWP among them is compared with the relative unit volume refrigeration capacity Qv (ratio of the unit volume refrigeration capacity with R290) , Relative coefficient of performance COP (ratio of coefficient of performance to R290), temperature slip, compressor discharge pressure and compressor discharge temperature.
  • Qv ratio of the unit volume refrigeration capacity with R290
  • COP ratio of coefficient of performance to R290
  • temperature slip temperature slip
  • compressor discharge pressure compressor discharge temperature
  • the GWP of the ternary refrigeration composition prepared in Examples 1 to 49 is less than 150, and has good environmental protection characteristics; the relative volumetric refrigeration capacity and relative coefficient of performance of all refrigerant formulations are greater than 0.95 ( Except Example 43 to Example 49), the refrigeration capacity and energy efficiency are basically the same as the use of R290 refrigerant; all refrigerants have better flammability than R290, the compressor discharge pressure is not much different from R290, and the discharge temperature is slightly higher.
  • the flammability of all the mixed refrigerants in the embodiment is lower than that of R290, and the higher the ratio of R32 and R1234yf in the mixture, the lower the flammability.
  • the GWP of each refrigerant formulation is low, the refrigeration capacity per unit volume and the system performance coefficient are similar to R290, and the flammability is improved.
  • the present invention can be better. To replace R290 refrigerant.

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Abstract

Provided by the present invention are a ternary refrigeration composition and a refrigeration device comprising same. The ternary refrigeration composition is composed of a first component and a second component, the first component being fluoroethane, and the second component being selected from any two among 1,1-difluoroethane, difluoromethane and 2,3,3,3-tetrafluoropropene. The environmental protection properties and the thermodynamic properties of fluoroethane are similar to those of R290 but the combustibility of fluoroethane is lower than that of R290, and fluoroethane and the second component having the combustibility of class 2 or 2L are used together, so that the refrigeration composition may have the characteristics of low GWP, good thermodynamic properties and a low combustibility grade, and the usage safety is improved. The ternary refrigeration composition has an ODP value of zero, i.e. does not damage the ozone layer even after long-term use. Therefore, the ternary refrigeration composition has a relatively low GWP, an ODP of 0, and two combustibility types, and when the ternary refrigeration composition is applied, the capacity and the energy efficiency of a unit are equivalent to those of a unit using an R290 refrigerant.

Description

三元制冷组合物及包含其的制冷装置Ternary refrigeration composition and refrigeration device containing the same 技术领域Technical field
本发明涉及制冷材料技术领域，具体而言，涉及一种三元制冷组合物及包含其的制冷装置。The present invention relates to the technical field of refrigeration materials, in particular to a ternary refrigeration composition and a refrigeration device containing the same.
背景技术Background technique
在全球变暖的背景下，制冷技术面临着“环保”和“节能”两大压力，寻找环保、高效的替代工质是制冷行业急需解决的关键问题。自然工质丙烷(R290)因具有零臭氧消耗潜值(ODP)、极低的全球变暖潜值(GWP)和良好的热力学性质，被认为是未来的替代制冷剂之一。R290在德国、瑞典等欧盟国家已应用于空气调节系统、冰箱和小型冷冻冷藏箱，印度也已经实现了R290空调的市场化。国内格力、美的和海尔等企业率先开展R290空调生产线改造项目，已建成多条生产线。但是R290属于3类易燃制冷剂，处于安全性的考虑，其无法在市场上进行大范围推广。In the context of global warming, refrigeration technology is facing two major pressures of "environmental protection" and "energy saving". Finding environmentally friendly and efficient alternative working fluids is a key issue that the refrigeration industry urgently needs to solve. Propane (R290), a natural working fluid, has zero ozone depletion potential (ODP), extremely low global warming potential (GWP) and good thermodynamic properties, so it is considered to be one of the future alternative refrigerants. R290 has been used in air-conditioning systems, refrigerators and small freezers in Germany, Sweden and other EU countries. India has also realized the marketization of R290 air conditioners. Domestic companies such as Gree, Midea and Haier took the lead in launching the R290 air-conditioning production line transformation project, and several production lines have been built. However, R290 is classified as a Class 3 flammable refrigerant, and for safety reasons, it cannot be widely promoted in the market.
鉴于上述问题的存在，有必要提供一种同时具有低GWP、ODP值为0，良好热力学性能以及安全性较高的制冷组合物。In view of the above-mentioned problems, it is necessary to provide a refrigeration composition that has a low GWP, an ODP value of 0, good thermodynamic properties, and high safety.
发明内容Summary of the invention
本发明的主要目的在于提供一种三元制冷组合物及包含其的制冷装置，以解决现有的制冷组合物无法在保证低GWP、低ODP和良好热力学性能的同时，还具有较低的可燃性能的问题。The main purpose of the present invention is to provide a ternary refrigeration composition and a refrigeration device containing the same, so as to solve the problem that the existing refrigeration composition cannot guarantee low GWP, low ODP and good thermodynamic properties while also having low flammability. Performance issues.
为了实现上述目的，根据本发明的一个方面，提供了一种三元制冷组合物，三元制冷组合物由第一组分和第二组分组成，其中第一组分为氟乙烷，第二组分选自1,1-二氟乙烷、二氟甲烷和2,3,3,3-四氟丙烯中的任意两种。In order to achieve the above objective, according to one aspect of the present invention, a ternary refrigeration composition is provided. The ternary refrigeration composition is composed of a first component and a second component, wherein the first component is fluoroethane, and the first component is fluoroethane. The two components are selected from any two of 1,1-difluoroethane, difluoromethane and 2,3,3,3-tetrafluoropropene.
进一步地，第二组分为1,1-二氟乙烷和二氟甲烷，以占三元制冷组合物的摩尔百分含量计，三元制冷组合物包括76～88％第一组分、4～20％1,1-二氟乙烷及4～12％二氟甲烷。Further, the second component is 1,1-difluoroethane and difluoromethane, and the ternary refrigeration composition includes 76-88% of the first component, calculated as a mole percentage of the ternary refrigeration composition, 4-20% 1,1-difluoroethane and 4-12% difluoromethane.
进一步地，以占三元制冷组合物的摩尔百分含量计，三元制冷组合物包括84～88％第一组分，4～12％1,1-二氟乙烷及4～12％二氟甲烷。Further, the ternary refrigeration composition includes 84 to 88% of the first component, 4 to 12% 1,1-difluoroethane and 4 to 12% of the ternary refrigeration composition in terms of mole percentage. Fluoromethane.
进一步地，以占三元制冷组合物的摩尔百分含量计，三元制冷组合物包括76～80％第一组分，12～20％1,1-二氟乙烷及4～8％二氟甲烷。Further, based on the mole percentage of the ternary refrigeration composition, the ternary refrigeration composition includes 76-80% of the first component, 12-20% of 1,1-difluoroethane and 4-8% of difluoroethane. Fluoromethane.
进一步地，第二组分为二氟甲烷和2,3,3,3-四氟丙烯，以占三元制冷组合物的摩尔百分含量计，三元制冷组合物包括68～88％第一组分、4～20％二氟甲烷，4～28％2,3,3,3-四氟丙烯。Further, the second component is difluoromethane and 2,3,3,3-tetrafluoropropene, and the ternary refrigeration composition includes 68-88% of the first Components: 4-20% difluoromethane, 4-28% 2,3,3,3-tetrafluoropropene.
进一步地，以占三元制冷组合物的摩尔百分含量计，三元制冷组合物包括68～88％第一组分，4～8％二氟甲烷以及余量的2,3,3,3-四氟丙烯。Further, based on the mole percentage of the ternary refrigeration composition, the ternary refrigeration composition includes 68 to 88% of the first component, 4 to 8% of difluoromethane and the balance 2,3,3,3 -Tetrafluoropropylene.
进一步地，第二组分为1,1-二氟乙烷和2,3,3,3-四氟丙烯，以占三元制冷组合物的摩尔百分含量计，三元制冷组合物包括60～88％第一组分、4～12％1,1-二氟乙烷和4～36％2,3,3,3-四氟丙烯。Further, the second component is 1,1-difluoroethane and 2,3,3,3-tetrafluoropropene. The ternary refrigeration composition includes 60% by mole percentage of the ternary refrigeration composition. ～88% of the first component, 4～12% of 1,1-difluoroethane and 4～36% of 2,3,3,3-tetrafluoropropene.
进一步地，以占三元制冷组合物的摩尔百分含量计，三元制冷组合物包括60～88％第一组分、4～8％1,1-二氟乙烷以及余量的2,3,3,3-四氟丙烯。Further, the ternary refrigeration composition includes 60-88% of the first component, 4-8% of 1,1-difluoroethane and the balance of 2, 3,3,3-Tetrafluoropropene.
本申请的另一方面还提供了一种制冷装置，该制冷装置包括制冷剂，且制冷剂包括本申请提供的三元制冷组合物。Another aspect of the present application also provides a refrigeration device. The refrigeration device includes a refrigerant, and the refrigerant includes the ternary refrigeration composition provided in the present application.
应用本发明的技术方案，氟乙烷(R161)的环保特性和热力学性能与R290相似，但可燃性低于R290，通过将氟乙烷与可燃性为2类或2L类的第二组分共同使用，能够使制冷组合物具有较低的GWP和良好热力学性能，以及较低的可燃性等级，提高其使用安全性；同时上述三元制冷组合物的ODP值为零，即使长期使用也不会造成对臭氧层的破坏。在此基础上，上述三元制冷组合物具有较低的GWP，ODP为0，可燃性为2类，且应用该三元制冷混合物的机组的能力和能效与使用R290制冷剂的机组相当。Using the technical solution of the present invention, the environmental protection characteristics and thermodynamic properties of fluoroethane (R161) are similar to R290, but the flammability is lower than R290. By combining fluoroethane with the second component whose flammability is Class 2 or Class 2L Use, can make the refrigeration composition have lower GWP and good thermodynamic properties, as well as lower flammability level, improve its safety; at the same time, the ODP value of the above-mentioned ternary refrigeration composition is zero, even if it is used for a long time. Cause damage to the ozone layer. On this basis, the above-mentioned ternary refrigeration composition has a lower GWP, ODP is 0, and the flammability is Class 2, and the capacity and energy efficiency of the unit using the ternary refrigeration mixture is equivalent to that of the unit using the R290 refrigerant.
具体实施方式Detailed ways
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。It should be noted that the embodiments in the application and the features in the embodiments can be combined with each other if there is no conflict. The present invention will be described in detail below in conjunction with embodiments.
正如背景技术所描述的，现有的制冷组合物无法在保证低GWP、低ODP和良好热力学性能的同时，还具有较低的可燃性能的问题。为了解决上述技术问题，本申请提供了一种三元制冷组合物，该三元制冷组合物由第一组分和第二组分组成，其中第一组分为氟乙烷，第二组分选自1,1-二氟乙烷、二氟甲烷和2,3,3,3-四氟丙烯中的任意两种。As described in the background art, the existing refrigeration composition cannot guarantee low GWP, low ODP and good thermodynamic properties, but also has the problem of low flammability. In order to solve the above-mentioned technical problems, the present application provides a ternary refrigeration composition consisting of a first component and a second component, wherein the first component is fluoroethane and the second component is Any two selected from 1,1-difluoroethane, difluoromethane and 2,3,3,3-tetrafluoropropene.
氟乙烷(R161)的环保特性和热力学性能与R290相似，但可燃性低于R290，通过将氟乙烷与可燃性为2类或2L类的第二组分共同使用，能够使制冷组合物具有较低的GWP和良好热力学性能，以及较低的可燃性等级，提高其使用安全性；同时上述三元制冷组合物的ODP值为零，即使长期使用也不会造成对臭氧层的破坏。在此基础上，上述三元制冷组合物具有较低的GWP，ODP为0，可燃性为2类，且应用该三元制冷混合物的机组的能力和能效与使用R290制冷剂的机组相当。The environmental protection characteristics and thermodynamic properties of fluoroethane (R161) are similar to R290, but the flammability is lower than R290. By using fluoroethane and the second component with flammability of class 2 or 2L together, the refrigeration composition can be made It has low GWP and good thermodynamic properties, and a low flammability level, which improves its safety in use; at the same time, the ODP value of the above-mentioned ternary refrigeration composition is zero, even if it is used for a long time, it will not cause damage to the ozone layer. On this basis, the above-mentioned ternary refrigeration composition has a lower GWP, ODP is 0, and the flammability is Class 2, and the capacity and energy efficiency of the unit using the ternary refrigeration mixture is equivalent to that of the unit using the R290 refrigerant.
二氟甲烷(R32)具有良好的热工性能，环保性能和安全性及市场获得性，但是单独作为制冷剂，R32会导致压缩机排气温度过高的问题。在一种优选的实施方式中，第二组分为1,1-二氟乙烷和二氟甲烷，以占三元制冷组合物的摩尔百分含量计，三元制冷组合物包括76～88％第一组分、4～20％1,1-二氟乙烷及4～12％二氟甲烷。将1,1-二氟乙烷和二氟甲烷的混合物作 为第二组分能够降低制冷过程中压缩机排气温度，同时将三元制冷组合物中各组分的用量限定在上述范围内有利于进一步提高三元制冷组合物的制冷效果，并降低其可燃性能。Difluoromethane (R32) has good thermal performance, environmental performance, safety and market availability, but as a refrigerant alone, R32 will cause the problem of excessive compressor discharge temperature. In a preferred embodiment, the second component is 1,1-difluoroethane and difluoromethane, and the ternary refrigeration composition includes 76-88 % First component, 4-20% 1,1-difluoroethane and 4-12% difluoromethane. Using the mixture of 1,1-difluoroethane and difluoromethane as the second component can reduce the compressor discharge temperature during the refrigeration process, and at the same time limit the amount of each component in the ternary refrigeration composition within the above range. It is beneficial to further improve the refrigeration effect of the ternary refrigeration composition and reduce its flammability.
更优选地，以占三元制冷组合物的摩尔百分含量计，三元制冷组合物包括84～88％第一组分，4～12％1,1-二氟乙烷及4～12％二氟甲烷；或者，以占三元制冷组合物的摩尔百分含量计，三元制冷组合物包括76～80％第一组分，12～20％1,1-二氟乙烷及4～8％二氟甲烷。针对第一组分的用量，更加精准地控制第二组分中1,1-二氟乙烷与二氟甲烷的用量，从而有利于进一步降低其可燃性，并提高其循环性能。More preferably, the ternary refrigeration composition comprises 84 to 88% of the first component, 4 to 12% 1,1-difluoroethane, and 4 to 12% based on the mole percentage of the ternary refrigeration composition. Difluoromethane; or, based on the mole percentage of the ternary refrigeration composition, the ternary refrigeration composition includes 76 to 80% of the first component, 12 to 20% of 1,1-difluoroethane and 4 to 8% difluoromethane. Regarding the amount of the first component, the amount of 1,1-difluoroethane and difluoromethane in the second component is more accurately controlled, so as to further reduce its flammability and improve its cycle performance.
在一种优选的实施方式中，第二组分为1,1-二氟乙烷和2,3,3,3-四氟丙烯，以占三元制冷组合物的摩尔百分含量计，三元制冷组合物包括60～88％第一组分、4～12％1,1-二氟乙烷和4～36％2,3,3,3-四氟丙烯。将1,1-二氟乙烷和2,3,3,3-四氟丙烯的混合物作为第二组分，同时将三元制冷组合物中各组分的用量限定在上述范围内有利于进一步提高三元制冷组合物的制冷效果，并降低其可燃性能。In a preferred embodiment, the second component is 1,1-difluoroethane and 2,3,3,3-tetrafluoropropene, and is calculated as a mole percentage of the ternary refrigeration composition. The primary refrigeration composition includes 60-88% of the first component, 4-12% of 1,1-difluoroethane and 4-36% of 2,3,3,3-tetrafluoropropene. Using the mixture of 1,1-difluoroethane and 2,3,3,3-tetrafluoropropene as the second component, while limiting the amount of each component in the ternary refrigeration composition within the above range is beneficial to further Improve the refrigeration effect of the ternary refrigeration composition and reduce its flammability.
为了进一步发挥第一组份和第二组分的性能优势，提升三元制冷组合物的性能，更优选地，以占三元制冷组合物的摩尔百分含量计，三元制冷组合物包括60～88％第一组分、4～8％1,1-二氟乙烷以及余量的2,3,3,3-四氟丙烯。In order to further exert the performance advantages of the first component and the second component and improve the performance of the ternary refrigeration composition, more preferably, the ternary refrigeration composition includes 60% by mole percentage of the ternary refrigeration composition. ～88% of the first component, 4～8% of 1,1-difluoroethane and the balance of 2,3,3,3-tetrafluoropropene.
在一种优选的实施方式中，第二组分为二氟甲烷和2,3,3,3-四氟丙烯，以占三元制冷组合物的摩尔百分含量计，三元制冷组合物包括68～88％第一组分、4～20％二氟甲烷，4～28％2,3,3,3-四氟丙烯。将1,1-二氟乙烷和2,3,3,3-四氟丙烯的混合物作为第二组分能够降低制冷过程中压缩机排气温度，并进一步降低GWP，提高其环保性能；同时将三元制冷组合物中各组分的用量限定在上述范围内能够结合第一组合和第二组分的自身性能，进一步提高三元制冷组合物综合性能。In a preferred embodiment, the second component is difluoromethane and 2,3,3,3-tetrafluoropropene, and the ternary refrigeration composition includes 68 to 88% of the first component, 4 to 20% of difluoromethane, 4 to 28% of 2,3,3,3-tetrafluoropropene. Using the mixture of 1,1-difluoroethane and 2,3,3,3-tetrafluoropropene as the second component can reduce the compressor discharge temperature during the refrigeration process, further reduce GWP, and improve its environmental performance; Limiting the amount of each component in the ternary refrigeration composition within the above range can combine the properties of the first combination and the second component, and further improve the overall performance of the ternary refrigeration composition.
为了进一步发挥第一组份和第二组分的性能优势，提升三元制冷组合物的性能，更优选地，以占三元制冷组合物的摩尔百分含量计，三元制冷组合物包括68～88％第一组分，4～8％二氟甲烷以及余量的2,3,3,3-四氟丙烯。In order to further exert the performance advantages of the first component and the second component and improve the performance of the ternary refrigeration composition, more preferably, the ternary refrigeration composition includes 68% by mole percentage of the ternary refrigeration composition. ～88% of the first component, 4～8% of difluoromethane and the balance 2,3,3,3-tetrafluoropropene.
本申请的另一方面还提供了一种制冷装置，制冷装置包括制冷剂，其中，制冷剂包括上述三元制冷组合物。Another aspect of the present application also provides a refrigeration device. The refrigeration device includes a refrigerant, wherein the refrigerant includes the above-mentioned ternary refrigeration composition.
上述三元制冷组合物具有较低的GWP，ODP为0，可燃性为2类。将其应用于制冷装置中能够获得较高的能力和能效，同时还能使制冷装置具有更高的安全性和环保性。The above-mentioned ternary refrigeration composition has lower GWP, ODP is 0, and flammability is Class 2. Applying it to the refrigeration device can obtain higher capacity and energy efficiency, and at the same time can make the refrigeration device have higher safety and environmental protection.
以下结合具体实施例对本申请作进一步详细描述，这些实施例不能理解为限制本申请所要求保护的范围。The application will be further described in detail below in conjunction with specific embodiments, and these embodiments should not be understood as limiting the scope of protection claimed by the application.
实施例中所涉及到的各组元的热物性如表1所示。The thermophysical properties of the components involved in the examples are shown in Table 1.
表1Table 1
Figure PCTCN2020120213-appb-000001
Figure PCTCN2020120213-appb-000001
各实施例制得的三元制冷组合物的组成见表2。The composition of the ternary refrigeration composition prepared in each example is shown in Table 2.
表2Table 2
序号Serial number 第一组分First component 第二组分aThe second component a 第二组分bSecond component b 摩尔配比Molar ratio
实施例1Example 1 R161R161 R152aR152a R32R32 0.76/0.16/0.080.76/0.16/0.08
实施例2Example 2 R161R161 R152aR152a R32R32 0.76/0.2/0.040.76/0.2/0.04
实施例3Example 3 R161R161 R152aR152a R32R32 0.8/0.12/0.080.8/0.12/0.08
实施例4Example 4 R161R161 R152aR152a R32R32 0.84/0.04/0.120.84/0.04/0.12
实施例5Example 5 R161R161 R152aR152a R32R32 0.84/0.08/0.080.84/0.08/0.08
实施例6Example 6 R161R161 R152aR152a R32R32 0.84/0.12/0.040.84/0.12/0.04
实施例7Example 7 R161R161 R152aR152a R32R32 0.88/0.04/0.080.88/0.04/0.08
实施例8Example 8 R161R161 R152aR152a R1234yfR1234yf 0.68/0.04/0.280.68/0.04/0.28
实施例9Example 9 R161R161 R152aR152a R1234yfR1234yf 0.68/0.08/0.240.68/0.08/0.24
实施例10Example 10 R161R161 R152aR152a R1234yfR1234yf 0.72/0.04/0.240.72/0.04/0.24
实施例11Example 11 R161R161 R152aR152a R1234yfR1234yf 0.72/0.08/0.20.72/0.08/0.2
实施例12Example 12 R161R161 R152aR152a R1234yfR1234yf 0.72/0.12/0.160.72/0.12/0.16
实施例13Example 13 R161R161 R152aR152a R1234yfR1234yf 0.72/0.16/0.120.72/0.16/0.12
实施例14Example 14 R161R161 R152aR152a R1234yfR1234yf 0.76/0.04/0.20.76/0.04/0.2
实施例15Example 15 R161R161 R152aR152a R1234yfR1234yf 0.76/0.08/0.160.76/0.08/0.16
实施例16Example 16 R161R161 R152aR152a R1234yfR1234yf 0.76/0.12/0.120.76/0.12/0.12
实施例17Example 17 R161R161 R152aR152a R1234yfR1234yf 0.76/0.16/0.080.76/0.16/0.08
实施例18Example 18 R161R161 R152aR152a R1234yfR1234yf 0.76/0.2/0.040.76/0.2/0.04
实施例19Example 19 R161R161 R152aR152a R1234yfR1234yf 0.8/0.04/0.160.8/0.04/0.16
实施例20Example 20 R161R161 R152aR152a R1234yfR1234yf 0.8/0.08/0.120.8/0.08/0.12
实施例21Example 21 R161R161 R152aR152a R1234yfR1234yf 0.8/0.12/0.080.8/0.12/0.08
实施例22Example 22 R161R161 R152aR152a R1234yfR1234yf 0.84/0.04/0.120.84/0.04/0.12
实施例23Example 23 R161R161 R152aR152a R1234yfR1234yf 0.84/0.08/0.080.84/0.08/0.08
实施例24Example 24 R161R161 R152aR152a R1234yfR1234yf 0.88/0.04/0.080.88/0.04/0.08
实施例25Example 25 R161R161 R32R32 R1234yfR1234yf 0.6/0.04/0.360.6/0.04/0.36
实施例26Example 26 R161R161 R32R32 R1234yfR1234yf 0.64/0.04/0.320.64/0.04/0.32
实施例27Example 27 R161R161 R32R32 R1234yfR1234yf 0.64/0.08/0.280.64/0.08/0.28
实施例28Example 28 R161R161 R32R32 R1234yfR1234yf 0.68/0.04/0.280.68/0.04/0.28
实施例29Example 29 R161R161 R32R32 R1234yfR1234yf 0.68/0.08/0.240.68/0.08/0.24
实施例30Example 30 R161R161 R32R32 R1234yfR1234yf 0.72/0.04/0.240.72/0.04/0.24
实施例31Example 31 R161R161 R32R32 R1234yfR1234yf 0.72/0.08/0.20.72/0.08/0.2
实施例32Example 32 R161R161 R32R32 R1234yfR1234yf 0.72/0.12/0.160.72/0.12/0.16
实施例33Example 33 R161R161 R32R32 R1234yfR1234yf 0.76/0.04/0.20.76/0.04/0.2
实施例34Example 34 R161R161 R32R32 R1234yfR1234yf 0.76/0.08/0.160.76/0.08/0.16
实施例35Example 35 R161R161 R32R32 R1234yfR1234yf 0.76/0.12/0.120.76/0.12/0.12
实施例36Example 36 R161R161 R32R32 R1234yfR1234yf 0.8/0.04/0.160.8/0.04/0.16
实施例37Example 37 R161R161 R32R32 R1234yfR1234yf 0.8/0.08/0.120.8/0.08/0.12
实施例38Example 38 R161R161 R32R32 R1234yfR1234yf 0.8/0.12/0.080.8/0.12/0.08
实施例39Example 39 R161R161 R32R32 R1234yfR1234yf 0.84/0.04/0.120.84/0.04/0.12
实施例40Example 40 R161R161 R32R32 R1234yfR1234yf 0.84/0.08/0.080.84/0.08/0.08
实施例41Example 41 R161R161 R32R32 R1234yfR1234yf 0.84/0.12/0.040.84/0.12/0.04
实施例42Example 42 R161R161 R32R32 R1234yfR1234yf 0.88/0.04/0.080.88/0.04/0.08
实施例43Example 43 R161R161 R152aR152a R32R32 0.70/0.12/0.180.70/0.12/0.18
实施例44Example 44 R161R161 R152aR152a R32R32 0.76/0.05/0.190.76/0.05/0.19
实施例45Example 45 R161R161 R152aR152a R32R32 0.80/0.04/0.160.80/0.04/0.16
实施例46Example 46 R161R161 R152aR152a R1234yfR1234yf 0.60/0.10/0.300.60/0.10/0.30
实施例47Example 47 R161R161 R152aR152a R1234yfR1234yf 0.70/0.26/0.040.70/0.26/0.04
实施例48Example 48 R161R161 R32R32 R1234yfR1234yf 0.50/0.20/0.300.50/0.20/0.30
实施例49Example 49 R161R161 R32R32 R1234yfR1234yf 0.60/0.10/0.300.60/0.10/0.30
以实施例1至49中的三元制冷组合物依替代R290作为空调制冷剂。所选取的设计工况为：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。分别使用上述实施例中的三元制冷组合物和R290制冷剂在制冷系统中的循环性能参数进行理论计算，比较了其中的GWP，相对单位容积制冷量Qv(与R290的单位容积制冷量比值)，相对性能系数COP(与R290的性能系数比值)，温度滑移，压缩机排气压力和压缩机排气温度。计算结果见表3。The ternary refrigeration composition in Examples 1 to 49 was used instead of R290 as the air-conditioning refrigerant. The selected design conditions are: the evaporator outlet temperature is 283.15K, the condenser outlet temperature is 313.15K, the gas phase at the evaporator outlet is in a superheated state, and the superheat is 5K, and the liquid phase at the condenser outlet is in a supercooled state. The cooling degree is 5K, and the adiabatic efficiency of the compressor is 0.75. The ternary refrigeration composition in the above-mentioned embodiment and the cycle performance parameters of R290 refrigerant in the refrigeration system are used for theoretical calculations, and the GWP among them is compared with the relative unit volume refrigeration capacity Qv (ratio of the unit volume refrigeration capacity with R290) , Relative coefficient of performance COP (ratio of coefficient of performance to R290), temperature slip, compressor discharge pressure and compressor discharge temperature. The calculation results are shown in Table 3.
表3table 3
Figure PCTCN2020120213-appb-000002
Figure PCTCN2020120213-appb-000002
Figure PCTCN2020120213-appb-000003
Figure PCTCN2020120213-appb-000003
由上表3可知，实施例1至49中制得的三元制冷组合物的GWP均小于150，具有较好的环保特性；所有制冷剂配方的相对容积制冷量和相对性能系数均大于0.95(实施例43至实施例49除外)，制冷能力和能效与使用R290制冷剂基本相当；所有制冷剂可燃性优于R290，压缩机排气压力与R290的相差不大，排气温度略高。同时由于可燃性上R290>R161>R152a>R32>R1234yf，因而实施例中所有混合制冷剂的可燃性都比R290低，且混合物中R32和R1234yf的比例越高，可燃性越低。It can be seen from Table 3 above that the GWP of the ternary refrigeration composition prepared in Examples 1 to 49 is less than 150, and has good environmental protection characteristics; the relative volumetric refrigeration capacity and relative coefficient of performance of all refrigerant formulations are greater than 0.95 ( Except Example 43 to Example 49), the refrigeration capacity and energy efficiency are basically the same as the use of R290 refrigerant; all refrigerants have better flammability than R290, the compressor discharge pressure is not much different from R290, and the discharge temperature is slightly higher. At the same time, due to the flammability of R290>R161>R152a>R32>R1234yf, the flammability of all the mixed refrigerants in the embodiment is lower than that of R290, and the higher the ratio of R32 and R1234yf in the mixture, the lower the flammability.
由上所述，在以上设计工况和以上理论计算的优选比例范围内，各制冷剂配方的GWP低，单位容积制冷量和系统性能系数与R290相近且可燃性得到改善，本发明能够较好的对R290制冷剂进行替代。From the above, in the above design conditions and the above theoretical calculation of the preferred ratio range, the GWP of each refrigerant formulation is low, the refrigeration capacity per unit volume and the system performance coefficient are similar to R290, and the flammability is improved. The present invention can be better. To replace R290 refrigerant.
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above are only preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

  1. 一种三元制冷组合物，其特征在于，所述三元制冷组合物由第一组分和第二组分组成，其中所述第一组分为氟乙烷，所述第二组分选自1,1-二氟乙烷、二氟甲烷和2,3,3,3-四氟丙烯中的任意两种。A ternary refrigeration composition, characterized in that, the ternary refrigeration composition is composed of a first component and a second component, wherein the first component is fluoroethane, and the second component is selected From any two of 1,1-difluoroethane, difluoromethane and 2,3,3,3-tetrafluoropropene.
  2. 根据权利要求1所述的三元制冷组合物，其特征在于，所述第二组分为所述1,1-二氟乙烷和所述二氟甲烷，以占所述三元制冷组合物的摩尔百分含量计，所述三元制冷组合物包括76～88％所述第一组分、4～20％所述1,1-二氟乙烷及4～12％所述二氟甲烷。The ternary refrigeration composition according to claim 1, wherein the second component is the 1,1-difluoroethane and the difluoromethane to account for the ternary refrigeration composition The ternary refrigeration composition includes 76 to 88% of the first component, 4 to 20% of the 1,1-difluoroethane and 4 to 12% of the difluoromethane .
  3. 根据权利要求2所述的三元制冷组合物，其特征在于，以占所述三元制冷组合物的摩尔百分含量计，所述三元制冷组合物包括84～88％所述第一组分，4～12％所述1,1-二氟乙烷及4～12％所述二氟甲烷。The ternary refrigeration composition according to claim 2, wherein the ternary refrigeration composition comprises 84-88% of the first group based on the mole percentage of the ternary refrigeration composition. In addition, 4-12% of the 1,1-difluoroethane and 4-12% of the difluoromethane.
  4. 根据权利要求2所述的三元制冷组合物，其特征在于，以占所述三元制冷组合物的摩尔百分含量计，所述三元制冷组合物包括76～80％所述第一组分，12～20％所述1,1-二氟乙烷及4～8％所述二氟甲烷。The ternary refrigeration composition according to claim 2, wherein the ternary refrigeration composition comprises 76-80% of the first group based on the mole percentage of the ternary refrigeration composition. In addition, 12-20% of the 1,1-difluoroethane and 4-8% of the difluoromethane.
  5. 根据权利要求1所述的三元制冷组合物，其特征在于，所述第二组分为所述二氟甲烷和所述2,3,3,3-四氟丙烯，以占所述三元制冷组合物的摩尔百分含量计，所述三元制冷组合物包括68～88％所述第一组分、4～20％所述二氟甲烷，4～28％所述2,3,3,3-四氟丙烯。The ternary refrigeration composition according to claim 1, wherein the second component is the difluoromethane and the 2,3,3,3-tetrafluoropropene to account for the ternary In terms of mole percentage of the refrigeration composition, the ternary refrigeration composition includes 68-88% of the first component, 4-20% of the difluoromethane, and 4-28% of the 2,3,3 ,3-Tetrafluoropropene.
  6. 根据权利要求5所述的三元制冷组合物，其特征在于，以占所述三元制冷组合物的摩尔百分含量计，所述三元制冷组合物包括68～88％所述第一组分，4～8％所述二氟甲烷以及余量的所述2,3,3,3-四氟丙烯。The ternary refrigeration composition of claim 5, wherein the ternary refrigeration composition comprises 68-88% of the first group based on the mole percentage of the ternary refrigeration composition. Divided into 4-8% of the difluoromethane and the balance of the 2,3,3,3-tetrafluoropropene.
  7. 根据权利要求1所述的三元制冷组合物，其特征在于，所述第二组分为所述1,1-二氟乙烷和所述2,3,3,3-四氟丙烯，以占所述三元制冷组合物的摩尔百分含量计，所述三元制冷组合物包括60～88％所述第一组分、4～12％所述1,1-二氟乙烷和4～36％所述2,3,3,3-四氟丙烯。The ternary refrigeration composition according to claim 1, wherein the second component is the 1,1-difluoroethane and the 2,3,3,3-tetrafluoropropene, and In terms of mole percentage of the ternary refrigeration composition, the ternary refrigeration composition includes 60-88% of the first component, 4-12% of the 1,1-difluoroethane, and 4 ~36% of the 2,3,3,3-tetrafluoropropene.
  8. 根据权利要求7所述的三元制冷组合物，其特征在于，以占所述三元制冷组合物的摩尔百分含量计，所述三元制冷组合物包括60～88％所述第一组分、4～8％所述1,1-二氟乙烷以及余量的所述2,3,3,3-四氟丙烯。The ternary refrigeration composition according to claim 7, wherein the ternary refrigeration composition comprises 60-88% of the first group based on the mole percentage of the ternary refrigeration composition. 4 to 8% of the 1,1-difluoroethane and the balance of the 2,3,3,3-tetrafluoropropene.
  9. 一种制冷装置，其特征在于，所述制冷装置包括制冷剂，其中，所述制冷剂包括权利要求1至8中任一项所述的三元制冷组合物。A refrigeration device, characterized in that the refrigeration device includes a refrigerant, wherein the refrigerant includes the ternary refrigeration composition according to any one of claims 1 to 8.
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