WO2011038570A1 - 一种制冷剂组合物 - Google Patents

一种制冷剂组合物 Download PDF

Info

Publication number
WO2011038570A1
WO2011038570A1 PCT/CN2010/001465 CN2010001465W WO2011038570A1 WO 2011038570 A1 WO2011038570 A1 WO 2011038570A1 CN 2010001465 W CN2010001465 W CN 2010001465W WO 2011038570 A1 WO2011038570 A1 WO 2011038570A1
Authority
WO
WIPO (PCT)
Prior art keywords
hfc
refrigerant
tetrafluoropropene
mass
hfo
Prior art date
Application number
PCT/CN2010/001465
Other languages
English (en)
French (fr)
Inventor
王鑫
庞峰
孙森
胡金正
Original Assignee
山东东岳化工有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 山东东岳化工有限公司 filed Critical 山东东岳化工有限公司
Publication of WO2011038570A1 publication Critical patent/WO2011038570A1/zh

Links

Classifications

    • 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
    • C09K2205/126—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

Definitions

  • the present invention relates to the field of refrigerants, and relates to a refrigerant composition, and more particularly to a refrigerant composition for use in an automotive air conditioning system instead of 1,1,1,2-tetrafluoroethane (HFC-134a).
  • HFC-134a 1,1,1,2-tetrafluoroethane
  • HFC-134a 1,1,1,2-tetrafluoroethane
  • GWP value greenhouse effect potential
  • C0 2 the operating conditions of automobile air conditioners are complex and changeable, and the amount of refrigerant leakage is large, which contributes a lot to global warming.
  • Auto air conditioners have thus become one of the first refrigeration and air conditioning equipments to disable high GWP refrigerants. .
  • the EU will ban new-produced automotive air conditioners from using refrigerants with a GWP greater than 150; in January 2011
  • the refrigerants with a GWP value greater than 150 will be phased out in the use of automotive air conditioners; from January 1, 2017, all automotive air conditioners will be banned from using GWP values greater than 150.
  • Refrigerants Therefore, the use of low-GWP refrigerants in the refrigeration and air-conditioning industry (especially automotive air-conditioning) has become a trend and inevitable, and research and development work on alternatives is extremely urgent.
  • HFC-134a replacement in automotive air conditioners is mainly carbon dioxide (C0 2 ), 1,1-difluoroacetamidine (HFC-152a), 2,3,3,3-tetrafluoropropene (HFO). -1234yf) and some mixed working solutions, but each has its own advantages and disadvantages, is still not ideal, and does not form a clear alternative direction.
  • the use of co 2 greenhouse effect potential is low, non-flammable, but it needs to redesign and optimize the system, high cost, high system pressure, low energy efficiency; less use of 1,1-difluoroethane (HFC-152a) system
  • HFC-152a 1,1-difluoroethane
  • High energy efficiency and low refrigerant cost but its flammability is strong, the secondary circuit system is required, and the compressor discharge temperature is high; the 2,3,3,3-tetrafluoropropene (HFO-1234yf) system is less modified.
  • the flammability is weak and the compressor discharge temperature is low, but its energy efficiency is low, the refrigeration capacity is small, and the refrigerant cost is high.
  • the slip temperature of the mixture is required to be as small as possible.
  • patent applications US20080026977 and CN200780035213.6 disclose a mixture of tetrafluoropropene and heptafluorobutene, but the sliding temperature is relatively high and the cost is high:
  • X discloses HFO-1234ze and a binary or multi-component mixture selected from the group consisting of HFC-152a, HFC-227ea, HFC-134a, HFC-125, but if it is used to replace HFC-134a, it has lower energy efficiency and lower cooling capacity.
  • patent application US20080075673 discloses a mixture of HFO-1234ze and hydrocarbon composition, but its sliding temperature is larger and flammability is stronger:
  • patent applications US20060019857 and CN200580019197.2 disclose a mixture I consisting of HFO-1234ze.
  • patent application CN200610049650.0 discloses a mixture of HFC-161 and HFC-152a
  • Application CN200610052120.1 discloses a HFC-161, HFC- 152a or HC-600a and HC-600 and other components of the mixture
  • patent applications US20060116310 and US20060025322 discloses mixtures of HFC-152a and CF 3 I thereof
  • Patent Application Publication CN200510119566.7 A mixture of CF 3 I, HC-600 and HC-600a
  • patent application US2003178597 discloses a mixture of HC-600a, HFC-152a and CO 2 :
  • Patent application JP 11199863 discloses CF 3 I, HC-600, HC- A mixture of 600a and HFC-152a;
  • Patent Application CN98101170.5 discloses a mixture of HFC-152a, HC-600 and HC-600a;
  • Patent Application WO 9529210 discloses a mixture of HFC-152a and HC-
  • the present invention aims to study the use of a refrigerant for replacing an HFC-134a in an automotive air conditioning system, so that the newly developed refrigerant substitute has the same physical properties as HFC-134a and the pipeline of the existing HFC-134a system. It is compatible with components, safe to use, and has high cooling efficiency, and it does not damage the atmospheric ozone layer.
  • the GWP value is as low as possible and has a very small slip temperature.
  • the refrigerant composition of the present invention replacing HFC-134a is composed of 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1,1-difluoroacetamidine (HFC-152a), wherein each component As follows, are all mass percentages:
  • 1,1-difluoroethane 50 ⁇ 5 ⁇ / ⁇ .
  • the refrigerant composition of the present invention which replaces HFC-134a has the following composition, all of which are mass percentages:
  • 1,1-difluoroacetamidine 40 ⁇ 10%.
  • the refrigerant composition of the present invention which replaces HFC-134a includes, in addition to 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1,1-difluoroacetamidine (HFC-152a), It also contains isobutyl hydrazine (HC-600a), in which the components are as follows, all of which are mass percentages:
  • HFO-1234yf 2,3,3,3-tetrafluoropropene (HFO-1234yf) in the above composition
  • the molecular formula is CH 2 CFCF 3
  • the molar mass is 114.04 g/mol
  • the normal boiling point is -29.35 ° C
  • the critical temperature is 94.7. . C
  • the critical pressure is 3.375 MPa.
  • 1,1-difluoroacetamidine HFC-152a
  • its molecular formula is CHF 2 CH 3
  • the molar mass is 66.05g/mol
  • the normal boiling point is -24.0'C
  • the critical temperature is 113.3 °C
  • the critical pressure is 4.52MPa.
  • Isobutane (HC-600a) has a molecular formula of CH(CH 3 ) 3 , a molar mass of 58.12 g/mol, a normal boiling point of -11.7 ° C, a critical temperature of 134.7 ° C, and a critical pressure of 3.63 MPa.
  • the refrigerant composition provided by the present invention is prepared by using 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1J-difluoroethane (HFC-152a), or 2, 3, 3, 3-tetrafluoropropene (HFO-1234yf), 1,1-difluoroethane (HFC-152a) and isobutane (HC-600a), which can be physically mixed in the liquid phase according to their corresponding ratios. .
  • Environmental performance Table 1 lists the environmental performance comparison between the present invention and HFC-134a. It can be seen that the ozone destruction potential (ODP) of the present invention is zero, does not damage the atmospheric ozone layer, and the greenhouse effect potential (GWP) is very low, less than 100, compared with HFC-134a, reducing the emission potential by more than 95%, meeting the current EU environmental protection requirements for automotive air conditioning refrigerants, and fully complying with the long-term environmental protection requirements of HFC-134a replacement.
  • ODP ozone destruction potential
  • GWP greenhouse effect potential
  • Table 2 lists the thermal parameters of the present invention compared to HFC-134a at an evaporation temperature of -1 Torr, a condensing temperature of 62 °C, and a superheat temperature of 10. C.
  • the pressure of the refrigerant on the evaporator side is slightly higher than that of HFC-134a, and the pressure of the refrigerant on the condenser side is higher than that of HFC-134a.
  • HFC-134a Slightly low, but very close to HFC-134a, which not only achieves a smaller compression ratio, reduces compressor power consumption, but also meets the pressure requirements of direct charge replacement; compressor discharge temperature is comparable to HFC-134a, non-destructive The long-term stable operation of the compressor; and, the sliding temperature of the present invention is very small, and can be considered as an azeotropic mixture, which not only enhances the heat exchange in the two devices, but also the composition of the mixture does not change when the leakage occurs. It is good for the maintenance and maintenance of car air conditioners.
  • Table 3 lists the thermal performance of the present invention compared with HFC-134a.
  • the COP value of the present invention is comparable to that of HFC-134a, which not only improves the energy efficiency of the replacement of HFC-134a by tetrafluoropropene, but also shows that some ratios are also exhibited.
  • volume cooling capacity is also equivalent to HFC-134a, which not only overcomes the shortage of low-temperature when tetrafluoropropene replaces HFC-134a, but also shows a larger cooling capacity.
  • the metal compatibility, the plastic material and the elastic material in the original HFC-134a system are compatible with the material compatibility test in accordance with international standards, and it is not necessary to replace the HFC-134a in the transition process.
  • Replacement system Ingredients and piping are compatible with the ester oil (POE) and the alcohol oil (PAG) used in the HFC-134a system, as verified by the lubricant compatibility test.
  • the ternary mixture is not only It is compatible with ester oils (POE) and alcohol oils (PAG) and is compatible with lower-priced mineral oils (MO).
  • the present invention is not only compatible with the piping and components of the existing HFC-134a system, but also requires no replacement of piping components and lubricating oil, and it is also possible to replace the lubricating oil with a lower-priced mineral oil (MO), which will greatly Reduce the cost of transitions in the HFC-134a replacement process.
  • MO lower-priced mineral oil
  • the present invention is equivalent to the physical properties of HFC-134a, compatible with the pipelines and components of the existing HFC-134a system, safe to use, has high refrigeration efficiency, very small slip temperature, and does not destroy.
  • the atmospheric ozone layer and GWP are very low, meeting the current EU environmental requirements for refrigerants, and also meeting the long-term development requirements of HFC-134a replacement. It is an ideal substitute for HFC-134a in automotive air conditioners. Best way to implement the invention
  • Example 1 50% by mass of 2,3,3,3-tetrafluoropropene and 50% by mass of 1,1-difluoroethane were physically mixed in a liquid phase to serve as a refrigerant.
  • Example 2 60% by mass of 2,3,3,3-tetrafluoropropene and 40% by mass of 1, difluoroacetic acid were physically mixed in a liquid phase to serve as a refrigerant.
  • Example 3 A mass percentage of 75% of 2,3,3,3-tetrafluoropropene and 25% by mass of 1,1-difluoroethane were physically mixed in a liquid phase to serve as a refrigerant.
  • Example 4 80% by mass of 2,3,3,3-tetrafluoropropene and 20% by mass of 1,1-difluoroacetic acid were physically mixed in a liquid phase to serve as a refrigerant.
  • Example 5 90% by mass of 2,3,3,3-tetrafluoropropene and 10% by mass of 1,1-difluoroacetic acid were physically mixed in a liquid phase to serve as a refrigerant.
  • Example 6 95% by mass of 2,3,3,3-tetrafluoropropene and 5% by mass of 1,1-difluoroacetic acid were physically mixed in a liquid phase to serve as a refrigerant.
  • Example 8 76% by mass of 2,3,3,3-tetrafluoropropene, 21% by mass of 1,1-difluoroethane and 3% by mass of isobutane in liquid phase It is physically mixed and used as a refrigerant.
  • Example 9 90% by mass of 2,3,3,3-tetrafluoropropene, 5% by mass of 1,1-difluoroethane and 5% by mass of isobutyl hydrazine in liquid phase It is physically mixed and used as a refrigerant.
  • the environmental parameters of the refrigerant of the above embodiment are under the conditions of evaporating temperature of -1 'C, condensing temperature of 62'C, superheating temperature of 10'C, supercooling temperature of 5 °C, and compressor efficiency of 80%.
  • the physical properties and thermal properties are listed in Table 4.
  • ODP ozone depletion potential
  • GWP greenhouse effect potential
  • the pressure of the evaporator-side refrigerant of the present invention is slightly higher than that of HFC-134a, and the pressure of the refrigerant on the condenser side is slightly lower than that of HFC-134a, but is very close to that of HFC-134a, so that not only less compression can be obtained.
  • the compressor consumes less work, and meets the pressure requirements of direct charge replacement:
  • the slip temperature of the present invention is very small, and can be considered as an azeotropic mixture, which not only enhances heat exchange in the two devices, but also occurs.
  • the composition of the mixture at the time of leakage can be considered to be unchanged, which is beneficial to the maintenance and maintenance of the automobile air conditioner.
  • the COP value of the invention is equivalent to that of HFC-134a, which not only improves the energy efficiency of the replacement of HFC-134a by tetrafluoropropene, but also shows that certain ratios also show a certain energy saving effect;
  • the volumetric refrigeration capacity is also equivalent to HFC-134a, which not only overcomes The shortage of low-temperature when tetrafluoropropene replaced HFC-134a, and some ratios also showed greater cooling capacity.
  • the present invention is compatible with metal materials, plastic materials, elastic materials, and the like in the original HFC-134a system:
  • the binary mixture of the present invention and the ester oil (POE) and alcohol oil (PAG) used in the HFC-134a system are compatible with the binary mixture of the present invention and the ester oil (POE) and alcohol oil (PAG) used in the HFC-134a system.
  • the ternary mixture is compatible not only with ester oils (POE) and alcoholic oils (PAG), but also with lower-priced mineral oils (MO). Therefore, the present invention is compatible not only with the piping and components of the existing HFC-134a system, but also without replacing the piping components and lubricating oil, and also replacing the lubricating oil with a lower-priced mineral oil (MO). Will greatly reduce the cost of transition in the HFC-134a replacement process.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Air-Conditioning For Vehicles (AREA)

Description

一种制冷剂组合物 技术领域
本发明属于制冷剂领域， 涉及一种制冷剂组合物， 尤其涉及一种应用于汽车空调*** 中替代 1，1,1，2-四氟乙烷 （HFC-134a) 的制冷剂组合物。 背景技术
1,1 , 1 ,2-四氟乙垸 （HFC-134a)广泛用于汽车空调以及其它一些制冷***等领域， 但由 于其温室效应潜能值（GWP值）较高， 为 C02的 1430倍， 且汽车空调运行工况复杂多变， 制冷剂泄漏量较大，因而对全球气候变暖的贡献较大,汽车空调也由此成了首批禁用高 GWP 值制冷剂的制冷空调设备之一。 根据欧盟己通过的含氟温室气体（F-gas)控制法规的要求： 自 2011年 1月 1 日起， 欧盟将禁止新生产的汽车空调使用 GWP值大于 150的制冷剂； 在 2011年 1月 1日至 2017年 1月 1日的六年间， 在用汽车空调将按比例逐步淘汰 GWP值大 于 150的制冷剂； 自 2017年 1月 1日起， 将禁止所有汽车空调使用 GWP值大于 150的制 冷剂。 因此， 制冷空调行业 （尤其是汽车空调） 使用低 GWP值的制冷剂成为趋势和必然， 开展有关替代品的研究开发工作迫在眉睫。
目前， 国际社会对汽车空调中 HFC-134a替代的研究方向主要是二氧化碳 （C02)、 1,1- 二氟乙垸（HFC-152a)、 2，3，3，3-四氟丙烯 ( HFO-1234yf) 和一些混合工质方案， 但这些方 案各有优缺点， 仍不是很理想， 也没有形成明确的替代方向。 其中， 使用 co2温室效应潜 能值低、 不可燃， 但其需要重新设计和优化***、 成本高、 ***压力高、 能效低； 使用 1,1- 二氟乙烷（HFC-152a) ***改造少、 能效高、 制冷剂成本低， 但其可燃性较强、 需要二次 回路***、 压缩机排气温度较高； 使用 2，3,3，3-四氟丙烯 （HFO-1234yf)***改造少、 可燃 性弱、 压缩机排气温度较低， 但其能效较低、 制冷量较小、 制冷剂成本高。 另外， 当选择 混合工质方案时， 除了需要综合考虑环保、 物性、 能效、 成本等因素外， 由于汽车空调制 冷剂泄漏量较大， 为了便于维护和保养， 需要混合物的滑移温度尽可能小。
现有混合工质替代技术中，专利申请 US20080026977和 CN200780035213.6公开了四氟 丙烯与七氟丁烯组成的混合物， 但其滑移温度较大、 成本较高： 专利申请 US20080308763、 US7524805 和 CN200580022108.X 公开了 HFO-1234ze 和选自 HFC-152a、 HFC-227ea、 HFC-134a、 HFC-125组成的二元或多元混合物， 但其若用来替代 HFC-134a时或能效较低、 冷量较小、或 GWP值较高、或滑移温度较大；专利申请 US20080075673公开了 HFO-1234ze 和碳氢化合物组成的混合物， 但其滑移温度较大、 可燃性较强： 专利申请 US20060022166 和 CN200580019019.X公幵了 HFO-1234yf与 HFO-1225yeZ组成的混合物，但其滑移温度较 大、成本较高； 专利申请 US20060019857和 CN200580019197.2公开了 HFO-1234ze和 CF3I 组成的混合物，但由于 CF3I的 ODP值最近被测定并不为零，故其混合物对大气臭氧层仍有 一定破坏作用；专利申请 US20060043331和 CN200580021136.X公开了 HFO-1234ze与 C02 组成的混合物， 但其若用来替代 HFC-134a时压力较高、 滑移温度较大。
另外， 专利申请 CN200610049650.0公开了 HFC-161和 HFC-152a组成的混合物； 专利 申请 CN200610052120.1公开了 HFC-161、 HFC- 152a和 HC-600a或 HC-600等组成的混合 物； 专利申请 US20060116310和 US20060025322公开了 HFC-152a和 CF3I组成的混合物； 专利申请 CN200510119566.7公开了 CF3I、 HC-600和 HC-600a组成的混合物； 专利申请 US2003178597公开了 HC-600a、 HFC-152a和 C02组成的混合物： 专利申请 JP11199863公 开了 CF3I、 HC-600, HC-600a和 HFC-152a组成的混合物； 专利申请 CN98101170.5公开了 HFC-152a、 HC-600和 HC-600a组成的混合物； 专利申请 WO9529210公开了 HFC-152a和 HC-600a组成的混合物。 这些混合物同 HFC-134a相比均具有较低的 GWP值， 但这些混合 物存在或有较强的可燃性， 或具有较大的滑移温度， 或与现有汽车空调***兼容不好， 或 效率较低， 或价格昂贵等问题。 发明内容
本发明旨在研究幵发一种用于汽车空调***中替代 HFC-134a的制冷剂，使新开发的制 冷剂替代物既要与 HFC-134a物性相当、 与现有 HFC-134a***的管路和部件兼容、 使用安 全， 又要有较高的制冷效率， 而且还要不破坏大气臭氧层， GWP值尽量低， 并有非常小的 滑移温度。
本发明的替代 HFC-134a的制冷剂组合物， 由 2，3，3，3-四氟丙烯 （HFO-1234yf)和 1，1- 二氟乙垸 （HFC-152a) 组成， 其中各组分如下， 均为质量百分比：
2，3，3，3-四氟丙烯： 50〜95%
1，1-二氟乙烷： 50〜5ο/ο 。
优选的， 本发明的替代 HFC-134a的制冷剂组合物， 组分如下， 均为质量百分比：
2，3，3,3-四氟丙烯： 60〜90%
1，1-二氟乙垸： 40〜10% 。
.而且， 本发明的替代 HFC-134a 的制冷剂组合物， 除了包括 2，3，3,3-四氟丙烯 (HFO-1234yf) 和 1,1-二氟乙垸 (HFC-152a) 外, 还含有异丁垸（HC-600a)， 其中各组分 如下， 均为质量百分比：
2，3，3，3-四氟丙烯： 50〜90%
1，1-二氟乙垸： 5~48%
异丁垸： 2〜5 /。 。
上述组分中的 2，3，3，3-四氟丙烯 （HFO-1234yf), 其分子式为 CH2CFCF3, 摩尔质量为 114.04g/mol, 正常沸点为 -29.35°C , 临界温度为 94.7。C , 临界压力为 3.375MPa。
1,1-二氟乙垸 （HFC-152a), 其分子式为 CHF2CH3, 摩尔质量为 66.05g/mol， 正常沸点 为 -24.0'C , 临界温度为 113.3°C， 临界压力为 4.52MPa。
异丁烷（HC-600a), 其分子式为 CH(CH3)3， 摩尔质量为 58.12g/mol， 正常沸点为 -11.7 °C , 临界温度为 134.7'C， 临界压力为 3.63MPa。
本发明提供的制冷剂组合物的制备方法， 是将 2,3,3,3-四氟丙烯 （HFO-1234yf) 和 1J- 二氟乙烷 (HFC-152a), 或者 2，3，3,3-四氟丙烯 （HFO-1234yf)、 1,1-二氟乙烷 (HFC-152a) 和异丁烷 （HC-600a)， 按其相应的配比在液相状态下进行物理混合即可。
本发明具有以下优点和有益效果：
a. 环境性能 表 1列出了本发明与 HFC-134a的环境性能比较， 可以看出， 本发明的臭氧破坏潜能值 (ODP ) 为零， 不会破坏大气臭氧层， 温室效应潜能值 （GWP) 非常低， 小于 100, 相比 HFC-134a减少了 95%以上的排放潜能， 满足当前欧盟对汽车空调制冷剂的环保要求， 也完 全符合 HFC-134a替代的长远发展环保要求。
表 1 环境性能比较
Figure imgf000004_0001
b. 热工参数：
表 2列出了本发明与 HFC-134a的热工参数比较， 在蒸发温度为 -1 Γ、 冷凝温度为 62 °C、 过热温度为 10。C、 过冷温度为 5°C及压縮机效率为 80%的试验工况下， 蒸发器侧制冷 剂的压力值较 HFC-134a略高，冷凝器侧制冷剂的压力值较 HFC-134a略低，但与 HFC-134a 均非常接近， 如此不仅可获得更小的压缩比， 减少压缩机耗功， 而且满足直接充灌替代的 压力要求； 压缩机排气温度与 HFC-134a相当， 无损于压缩机的长期稳定运行； 并且， 本发 明的滑移温度非常小， 可以认为是一种共沸混合物， 不仅可增强两器中的换热， 而且发生 泄漏时混合物的组成可认为不发生变化， 有益于汽车空调的保养和维护。
热工参数比较
Figure imgf000004_0002
C. 热工性能
表 3列出了本发明与 HFC-134a的热工性能比较， 本发明的 COP值与 HFC-134a相当， 不仅提高了四氟丙烯替代 HFC-134a的能效， 而且某些配比还表现出了一定的节能效果； 容 积制冷量与 HFC-134a也相当， 不仅克服了四氟丙烯替代 HFC-134a时冷量低的不足， 而且 某些配比还表现出了更大的制冷量。
热工性能比较
Figure imgf000004_0003
d. 直接充灌性能
并且， 经过符合国际标准规定的材料相容性试验验证， 本发明与原 HFC-134a***中的 金属材料、塑性材料和弹性材料等均是相容的， 在替代 HFC-134a的转轨过程中无需更换系 统的部件和管路： 另外， 经润滑油相溶性试验验证， 本发明的二元混合物与 HFC-134a*** 使用的酯类油 （POE)和醇类油 （PAG)相溶， 三元混合物不仅与酯类油 （POE)和醇类油 (PAG)相溶， 而且与价格更低的矿物油（MO)相溶。 因此， 本发明不仅与现有 HFC-134a ***的管路和部件兼容， 无需更换管路部件和润滑油， 而且还可以把润滑油更换为价格更 低的矿物油 （MO), 这样将会大大降低 HFC-134a替代过程中的转轨费用。
综上所述， 本发明与 HFC-134a的物性相当、与现有 HFC-134a***的管路和部件兼容、 使用安全， 又具有较高的制冷效率、 非常小的滑移温度， 而且不破坏大气臭氧层、 GWP值 非常低， 满足当前欧盟对制冷剂的环保要求， 也符合 HFC-134a替代的长远发展要求， 替代 转轨费用低， 是汽车空调中 HFC-134a的一种理想替代品。 实施本发明的最佳方式
为了有助于对本发明所述的制冷剂及其优点的理解， 下面举出几个具体实施例， 其中 各组分的比例均为质量百分比。
实施例 1 : 将质量百分比 50%的 2,3,3,3-四氟丙烯和质量百分比 50%的 1，1-二氟乙烷两 种物质在液相下进行物理混合后作为制冷剂。
实施例 2: 将质量百分比 60%的 2,3，3，3-四氟丙烯和质量百分比 40%的 1， 二氟乙垸两 种物质在液相下进行物理混合后作为制冷剂。
实施例 3 : 将质量百分比 75%的 2,3,3,3-四氟丙烯和质量百分比 25%的 1,1-二氟乙烷两 种物质在液相下进行物理混合后作为制冷剂。
实施例 4: 将质量百分比 80%的 2，3，3,3-四氟丙烯和质量百分比 20%的 1，1-二氟乙垸两 种物质在液相下进行物理混合后作为制冷剂。
实施例 5: 将质量百分比 90%的 2,3,3,3-四氟丙烯和质量百分比 10%的 1，1-二氟乙垸两 种物质在液相下进行物理混合后作为制冷剂。
实施例 6: 将质量百分比 95%的 2,3,3,3-四氟丙烯和质量百分比 5%的 1,1-二氟乙垸两种 物质在液相下进行物理混合后作为制冷剂。
实施例 Ί: 将质量百分比 50%的 2,3,3,3-四氟丙稀、 质量百分比 48%的 1，1-二氟乙烷和 质量百分比 2%的异丁垸三种物质在液相下进行物理混合后作为制冷剂。
实施例 8: 将质量百分比 76%的 2，3，3，3-四氟丙烯、 质量百分比 21%的 1，1-二氟乙烷和 质量百分比 3%的异丁烷三种物质在液相下进行物理混合后作为制冷剂。
实施例 9: 将质量百分比 90%的 2，3，3，3-四氟丙烯、 质量百分比 5%的 1,1-二氟乙烷和质 量百分比 5%的异丁垸三种物质在液相下进行物理混合后作为制冷剂。
在蒸发温度为 -l 'C、 冷凝温度为 62'C、 过热温度为 10'C、 过冷温度为 5°C及压缩机效 率为 80%的工况下， 上述实施例制冷剂的环境参数、 物性参数及热工性能列于表 4中。
Figure imgf000006_0001
备注： *表示与 HFC-134a的相应比值， 其中 COP为性能系数。 从表 4可以看出本发明与 HFC-134a的各项参数和性能比较， 本发明的臭氧破坏潜能值 (ODP) 为零， 不会破坏大气臭氧层， 温室效应潜能值（GWP ) 非常低， 小于 100。
本发明的蒸发器侧制冷剂的压力值较 HFC-134a 略高， 冷凝器侧制冷剂的压力值较 HFC-134a略低， 但与 HFC-134a均非常接近， 如此不仅可获得更小的压缩比， 减少压缩机 耗功， 而且满足直接充灌替代的压力要求： 并且， 本发明的滑移温度非常小， 可以认为是 一种共沸混合物， 不仅可增强两器中的换热， 而且发生泄漏时混合物的组成可认为不发生 变化， 有益于汽车空调的保养和维护。
本发明的 COP值与 HFC-134a相当， 不仅提高了四氟丙烯替代 HFC- 134a的能效， 而且 某些配比还表现出了一定的节能效果； 容积制冷量与 HFC-134a也相当， 不仅克服了四氟丙 烯替代 HFC-134a时冷量低的不足， 而且某些配比还表现出了更大的制冷量。
本发明与原 HFC-134a***中的金属材料、 塑性材料和弹性材料等相容： 另外， 本发明 的二元混合物与 HFC-134a***使用的酯类油 （POE)和醇类油 （PAG) 相溶， 三元混合物 不仅与酯类油 （POE) 和醇类油 （PAG)相溶， 而且与价格更低的矿物油 （MO)相溶。 因 此， 本发明不仅与现有 HFC-134a***的管路和部件兼容， 替代时无需更换管路部件和润滑 油， 而且还可以把润滑油更换为价格更低的矿物油 （MO), 这样将会大大降低 HFC-134a 替代过程中的转轨费用。

Claims

权 利 要 求 书
1. 一种替代 HFC-134a的制冷剂组合物， 其特征在于该制冷剂含有 2，3,3，3-四氟丙烯和 1,1- 二氟乙垸两种物质， 其组分含量分别为：
2,3，3,3-四氟丙烯： 50〜95%
1,1-二氟乙烷： 50〜5ο/ο
均为质量百分比。
2. 如权利要求 1所述的种替代 HFC-134a的制冷剂组合物， 包括：
2,3,3,3-四氟丙烯： 60〜90%
1,1-二氟乙烷： 40〜10%
均为质量百分比。
3. 如权利要求 1所述的替代 HFC-134a的制冷剂组合物， 其特征在于该制冷剂还含有异丁 垸， 其组分含量分别为：
2，3，3,3-四氟丙烯： 50〜90%
1,1-二氟乙垸： 5~48°/0
异丁垸： 2〜5%
均为质量百分比。
4. 如权利要求 1或 3所述的替代 HFC-134a的制冷剂组合物的制备方法， 是将 2,3,3,3-四氟 丙烯 (HFO-1234yf) 和 1，1-二氟乙烷 (HFC-152a), 或者 2,3,3，3-四氟丙烯 （HFO-1234yf)、 1,1-二氟乙垸（HFC-152a) 和异丁烷 （HC-600a), 按其相应的配比在液相状态下进行物理 混合即可。
PCT/CN2010/001465 2009-09-29 2010-09-21 一种制冷剂组合物 WO2011038570A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN200910018489A CN101671542A (zh) 2009-09-29 2009-09-29 一种制冷剂组合物
CN200910018489.4 2009-09-29

Publications (1)

Publication Number Publication Date
WO2011038570A1 true WO2011038570A1 (zh) 2011-04-07

Family

ID=42018967

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2010/001465 WO2011038570A1 (zh) 2009-09-29 2010-09-21 一种制冷剂组合物

Country Status (2)

Country Link
CN (1) CN101671542A (zh)
WO (1) WO2011038570A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10174235B2 (en) 2017-03-01 2019-01-08 Haier Us Appliance Solutions, Inc. Low global warming potential binary refrigerant mixture with comparable energy efficiency to R-134a and a lower heat of combustion

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104232022A (zh) 2013-06-21 2014-12-24 中化蓝天集团有限公司 一种混合制冷剂
CN104277765B (zh) 2013-07-05 2017-12-08 中化蓝天集团有限公司 一种环保型近共沸混合制冷剂
CN105038711A (zh) * 2015-07-30 2015-11-11 天津大学 一种含有1,1-二氟乙烷的混合制冷剂
CN106893557B (zh) * 2015-12-18 2020-03-03 浙江省化工研究院有限公司 一种传热组合物及其应用
CN107057647A (zh) * 2017-06-21 2017-08-18 合肥嘉仕诚能源科技有限公司 一种用于空调的制冷剂及其制备方法
CN113366274A (zh) * 2019-01-30 2021-09-07 大金工业株式会社 库内空气调节装置
CN111253912B (zh) * 2020-03-20 2021-02-26 珠海格力电器股份有限公司 一种替换r290的环保混合制冷剂
CN113025279B (zh) * 2021-02-09 2023-07-25 浙江衢化氟化学有限公司 一种含有氟代烯烃的组合物及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101297016A (zh) * 2005-03-04 2008-10-29 纳幕尔杜邦公司 包含氟代烯烃的组合物
JP2009155463A (ja) * 2007-12-26 2009-07-16 Nippon Oil Corp 冷凍機油および冷凍機用作動流体組成物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101297016A (zh) * 2005-03-04 2008-10-29 纳幕尔杜邦公司 包含氟代烯烃的组合物
JP2009155463A (ja) * 2007-12-26 2009-07-16 Nippon Oil Corp 冷凍機油および冷凍機用作動流体組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10174235B2 (en) 2017-03-01 2019-01-08 Haier Us Appliance Solutions, Inc. Low global warming potential binary refrigerant mixture with comparable energy efficiency to R-134a and a lower heat of combustion

Also Published As

Publication number Publication date
CN101671542A (zh) 2010-03-17

Similar Documents

Publication Publication Date Title
WO2011038570A1 (zh) 一种制冷剂组合物
JP6017437B2 (ja) 低ｇｗｐの熱伝達組成物
CN101235275B (zh) 一种新型环保型制冷剂
JP2024075740A (ja) 冷媒組成物およびその使用
JP2014514423A (ja) 熱伝達組成物及び方法
EP3012307B1 (en) Mixed refrigerant
CN110878196B (zh) 一种四元混合环保制冷剂及组合物
JP2016514187A (ja) 冷却のための組成物および方法
CN110699043A (zh) 一种环保混合制冷工质
KR20150093728A (ko) 낮은 ｇｗｐ 열 전달 조성물
CN110878195A (zh) 一种含三氟碘甲烷的冷媒和含有其的混合物和换热***
WO2011035546A1 (zh) 一种环保制冷剂
CN112760080B (zh) 一种混合制冷剂和空调***
CN101735774A (zh) 一种替代r410a的环保制冷剂
CN102241962A (zh) 一种低gwp值的组合物
CN102229793A (zh) 一种低gwp值的制冷剂
CN112940683A (zh) 一种环保型制冷组合物
CN102229794A (zh) 一种低gwp值的制冷剂组合物
CN113563847B (zh) 四元环保混合制冷剂、其制备方法及制冷***
CN106543963B (zh) 一种环保型制冷组合物
CN100489051C (zh) 一种三元混合制冷剂组合物
CN101775268A (zh) 一种替代r410a的制冷剂组合物
CN110628388B (zh) 一种适用涡旋式压缩机的混合工质和汽车空调***
WO2022105274A1 (zh) 一种新型环保制冷剂及其制备方法
CN113637458A (zh) 制冷工质、制冷装置及应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10819799

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10819799

Country of ref document: EP

Kind code of ref document: A1